1. Field of the Invention
The present invention relates to a method for manufacturing an active component of surfactant, a surfactant containing the same, and a method for using the surfactant. In particular, the present invention relates to a method for manufacturing colloid particles composed of silicon oxides having the structural characteristics by calcining at a high temperature, a novel colloidal active component of surfactant made of compounds containing the same, and a method for using the surfactant.
2. Background of the Related Art
An ecological environment for a human, in spite of the various industrially developed structures thereof, is now in a danger of ecological crisis due to heavy pollution in rivers and lands caused by chemical abuse, and pollution in the atmosphere caused by harmful chemicals and products from side reactions. Human beings have enjoyed their much success in technical developments for synthesizing or manufacturing every kind of materials for the convenience of a life. However, they failed to notice the importance of environmentally-friendly technologies and thus, the technologies for decomposing and recycling wastes have been consequently neglected.
Among other many well-known pollutants, effluent from surfactants and detergents are the chief factors in water and land pollution. Typically used detergents contain polypropylene benzene sulfonate type alkyl compounds as a main component (ABS: Alkyl Benzene Sulfonate), which was later discovered to cause very severe water pollution in an ecological sense, and further being harmful to a human body. Therefore, linear alkyl benzene sulfonate (LABS) soon replaced as an attempt to solve the water pollution problems. Unfortunately, however, the LABS was much more toxic compared to ABS although it had higher water solubility. Moreover, when used alone, the conventional detergents, e.g., sulfates or sulfonates, were not very effective as far as the cleansing mechanism is concerned, thus other additives, e.g., a capturing agent, a precipitation promoter, or a chelating agent had to be added.
Consequently, the conventional detergents were blamed for causing dermatitis by releasing a great amount of additives, including submicron calcium carbonate, NTA (nitrilo triacetic acid) containing triple sodium phosphate, HEDTA (hexamethylene diamine tetraacetic acid), DTPA (dimethylene triamine pentaacetic acid). In addition, they created a main factor in slowing down biological decomposition, i.e., a biological stimulant in the water, causing eutrophication, which deterred the water""s self-cleansing action. Overall, they brought a severe pollution in water and public sanitation.
As an attempt to solve the problems described above, highly biodegradable detergents by microorganisms, having fatty acid type surfactants as a base, were introduced since they are known to have a relatively high safety in ecological prospect. However, the high degree of biodegradation of detergents was proved to be existing merely in theory, and it was not strong enough or appropriate for the current environment with a number of various nasty pollutants therein. Rather, the detergents play an important role for a polymerization linkage and worsen the pollution also. Interestingly, other developed nations have already banned or restricted the use of the detergents since it was discovered that the detergents are carsenogenic to a human, and have an estrogenic effect.
Accordingly, researches have been progressed for developing surfactants that are ecologically very safe and environmentally-friendly, and developing additives or builders that are essential for detergent formulation, but not much success has been made.
Accordingly, the present invention is directed to a method for manufacturing an active component of surfactant, surfactant and a method for using the surfactant that substantially obviate one or more problems due to limitations and disadvantages of the related art.
An object of the present invention is to provide a novel colloid active component for solving water and land pollution, and at the same time, being safe to a human and the ecosystem, so that it can be a versatile material in many fields, particularly, adding economic value and applicability to an industrial use.
Another object of the present invention is to provide a method for manufacturing colloid aluminum silica gel, comprising the steps of:
(a) dissolving a mixing solution of aluminum hydroxide in sulfuric acid, wherein the mixture includes aluminum oxide, silicic acid, potassium, iron oxide, sulfuric acid and water;
(b) adding potassium sulfate solution into the solution from (a), and stirring the mixture at a low temperature to produce compositions containing soluble aluminum double salt;
(c) purifying the compositions of the step (b) to obtain aluminum potassium sulfate with high purity and density;
(d) adding aluminum silicate and water to the aluminum potassium sulfate of the step (c) to produce alkali metal polysilicate-sulfate water salt chelate;
(e) polymerizing and precipitating the alkali metal polysilicate-sulfate water salt chelate at a low temperature to produce pectograph of aluminum silicate sieve;
(f) producing chelate by adding magnesia, iron oxide, calcium hydroxide, sodium oxide, potassium oxide, and distilled water in sequence;
(g) purifying and drying the chelate of the step (f) to produce dried microsphere;
(h) melting the dried microsphere of the step (g) at a high temperature, cooling, hardening, and mixing with diluted (thin) sulfuric acid;
(i) carrying out sequential treatments on the resultant of the step (h), that is, polymerizing, cleansing, heating, dehydrating, or drying, and performing vapor treatment, to obtain powder aluminum silicate molecular sieve with a high absorption of which particle size is under 1xcexc; and,
(j) polymerizing the aluminum silicate molecular sieves with each other until they are matured to be a highly dense heel.
The step (c) can be replaced with a cleansing step, in which the compositions are continuously heated and stirred, and 0.1% of enzyme by weight is slowly dropped thereto.
As for the step (d), aluminum sulfate and aluminum silicate can be mixed at a ratio of 1:3 by weight, and water was added to produce 24-water salt alkali metal polysilicate-sulfate chelates.
In addition, a preferred method for manufacturing the aforementioned colloid aluminum silica gel further comprises a step, in which the matured heel from the step (j) passes through an ion-exchange resin layer several times to produce very pure and consistent colloid aluminum silica gel, and later the consistent colloid is crushed.
Still another object of the present invention is to provide a surfactant having characteristic of both silica and alumina, being void of any chemical bond to form polymers by reacting with other molecules in the ecosystem, having an ability of metal substitution of zeolite at a low temperature, and containing evenly purified colloid aluminum silica gel having the particle size within a range of from several nm to several xcexcm for a diameter.
Here, the colloid aluminum silica gel can be manufactured by a process comprising the steps of:
(a) dissolving a mixing solution of aluminum hydroxide in sulfuric acid, wherein the mixture includes aluminum oxide, silicic acid, potassium, iron oxide, sulfuric acid and water;
(b) adding potassium sulfate solution into the solution from (a), and stirring the mixture at a low temperature to produce compositions containing soluble aluminum double salt;
(c) purifying the compositions of the step (b) to obtain aluminum potassium sulfate with high purity and density;
(d) adding aluminum silicate and water to the aluminum potassium sulfate of the step (c) to produce alkali metal polysilicate-sulfate water salt chelate;
(e) polymerizing and precipitating the alkali metal polysilicate-sulfate water salt chelate at a low temperature to produce pectograph of aluminum silicate sieve;
(f) producing chelate by adding magnesia, iron oxide, calcium hydroxide, sodium oxide, potassium oxide, and distilled water in sequence;
(g) purifying and drying the chelate of the step (f) to produce dried microsphere;
(h) melting the dried microsphere of the step (g) at a high temperature, cooling, hardening, and mixing with diluted (thin) sulfuric acid;
(i) carrying out sequential treatments on the resultant of the step (h), that is, polymerizing, cleansing, heating, dehydrating, or drying, and performing vapor treatment, to obtain powder aluminum silicate molecular sieve with a high absorption of which particle size is under 1xcexc; and,
(j) polymerizing the aluminum silicate molecular sieves with each other until they are matured to be a highly dense heel.
The steps (c) and (d) are similar to those of the above described method for manufacturing colloid aluminum silica gel. Likewise, the method can further comprise a step, in which the matured heel from the step (j) passes through an ion-exchange resin layer several times to produce very pure and consistent colloid aluminum silica gel, and later the consistent colloid is crushed.
A preferred surfactant containing colloid aluminum silica gel includes protecting colloid for ionizing strongly negative charges. The protecting colloid can be phycocolloid prepared by extract mucilage of brown seaweed in the ocean. The phycocolloid is one of botanical polysaccharides, and has a formula of C6H12O6)n, in which D(+) mannose as a main component possesses more than 9 glycosidic linkage.
The surfactant containing colloid aluminum silica gel preferably contains a little amount of photocatalyst that exhibits electro deposit in a titer solution. The electro deposit photocatalyst is selected from a group consisting cadmium chloride having a formula, Cd(ClO4)2.26H2O, cyclic ether, e.g., tetrahydrofuran, and cadmium sulfide colloid active sieve that is prepared by mixing a long ring-chain alkanethiol with sulfured hydrogen and dehydration drying.
Still another object of the present invention is to provide a surfactant containing alkanol amide condensate obtained from a reaction of 12-hydroxy-cis-9-octadecanoic acid, alkanol amine and water.
The above 12-hydroxy-cis-9-octadecanoic acid is preferably botanical ricinoleic acid which is extracted from caster oil and has a formula C18H34O3.
In addition, the surfactant containing the aforementioned alkaolamide condensate can have a little amount of photocatalyst that exhibits electro deposit in a titer solution The electro deposit photocatalyst is selected from a group consisting cadmium chloride having a formula, Cd(ClO4)2.26H2O, cyclic ether, e.g., tetrahydrofuran, and cadmium sulfide colloid active sieve that is prepared by mixing a long ring-chain alkanethiol with sulfured hydrogen and dehydration drying.
Still another object of the present invention is to provide a surfactant that forms spherical monodisperse colloid micell, which contains a homogeneous mixture consisting of nonionic surfactant of iso octylphenoxy polyoxy ethylene ethanol, a kind of ester of polyhydric alcohol and fatty acids having a formula of (CH3)3CCH2C(CH3)2C6H4O(OC2H4O)7(C2H4OH), a nonionic surfactant of p-tert-octylphenoxy polyethoxy ethanol having a formula of (CH3)3CCH2C(CH2)3C6H4O(CH2CH2O)XH, an nonionic surfactant having a formula of HOCH2(CH2CH2O)nCH2OH, polyoxy ethylene, and distilled water.
A preferred surfactant that can form spherical monodisperse collide micell contains a little amount of photocatalyst that exhibits electro deposit in a titer solution. The electro deposit photocatalyst is selected from a group consisting cadmium chloride having a formula, Cd(ClO4)2.26H2O, cyclic ether, e.g., tetrahydrofuran, and cadmium sulfide colloid active sieve that is prepared by mixing a long ring-chain alkanethiol with sulfured hydrogen and dehydration drying.
In short, the present invention provides a surfactant consisting of (1) 8 to 12 parts of colloid aluminum silica gel which has characteristics of both silica and alumina, being void of any chemical bond to form polymers by reacting with other molecules in an ecosystem, having a capacity of metal substitution of zeolite at a low temperature, and containing evenly purified colloid aluminum silica gel having the particle size within a range of from several nm to several xcexcm of diameter; (2) 5 to 8 parts of alkanol amide condensate obtained from a reaction of 12-hydroxy-cis-9-octadecanoic acid, alkanol amine and water; (3) 3 to 3.5 parts of nonionic surfactant of iso octylphenoxy polyoxy ethylene ethanol, a kind of ester of polyhydric alcohol and fatty acids having a formula of (CH3)3CCH2C(CH3)2C6H4O(OC2H4O)7(C2H4OH); (4) 2 to 2.3 parts of nonionic surfactant of p-tert-octylphenoxy polyethoxy ethanol having a formula of (CH3)3CCH2C(CH2)3C6H4O(CH2CH2O)XH; (5) 2.2 to 3 parts of phycocolloid, one of botanical polysaccharides, having a chemical formula of (C6H12O6)n and D(+) mannose as a main component possesses more than 9 glycosidic linkage; and (6) 70.90 to 79.30 parts of distilled water.
Preferably, the above surfactant further comprises 0.5 to 0.8% of electro deposit photocatalyst. The electro deposit photocatalyst is selected from a group consisting cadmium chloride having a formula, Cd(ClO4)2.26H2O, cyclic ether, e.g., tetrahydrofuran, and cadmium sulfide colloid active sieve that is prepared by mixing a long ring-chain alkanethiol with sulfured hydrogen and dehydration drying. More preferably, 5 to 7 wt % of the final mixture of the surfactant can be further dehydrated at the end.
The compositions of the surfactant according to the present invention can be effectively used for removing oil or grease; regenerating land polluted by hydrocarbon compounds; suppressing or removing red tide; cleansing a ship, airplane or automobile; decomposing a serum or hemoglobin; cleansing a fisherboat equipment or fishing net; catching light water ions; decomposing dextrine (starch), protein or denatured forms of the same; deinking treatment of waste prints; scouring textile, pulp, or wool; removing bacteria or mold; removing odor; cleansing equipment associated with water and vapor circulation; ultrasonic cleansing of iron or nonferrous metals; washing fabrics or furs; washing glasses or ceramics; bathing fur animals; collecting dust; pressure cleaning; or removing nicotine.
Moreover, the surfactant of the present invention can be added to cements, and table adopting agent or diesel materials to form cleansing solvent emulsifiers.
In the meantime, the surfactant compositions of the present invention can be included to cutting oil or lube. Also, the surfactant compositions can be used for washing any table cloth in the field of food processing. Further, the surfactant compositions are very useful for cleansing denatured water-soluble pollutants, neutral oil pollutants or glass fatty acids pollutants as well as washing nylon, cotton or wool.
Additional advantages, objects, and features of the invention will be set forth in part in the description which follows and in part will become apparent to those having ordinary skill in the art upon examination of the following or may be learned from practice of the invention. The objectives and other advantages of the invention may be realized and attained by the structure particularly pointed out in the written description and claims hereof as well as the appended drawings.
It is to be understood that both the foregoing general description and the following detailed description of the present invention are exemplary and explanatory and are intended to provide further explanation of the invention as claimed.
Reference will now be made in detail to the preferred embodiments of the present invention, examples of which are illustrated in the accompanying Chemical Formulas. The matters defined in the description are nothing but the ones provided to assist in a comprehensive understanding of the invention. Also, well-known functions or constructions are not described in detail since they would obscure the invention in unnecessary detail.
Inventors of the present invention discovered that the conventional alkyl benzene sulfonate (ABS) and linear alkyl benzene sulfonate (LABS) detergents are not easily decomposed by microorganism in the water, or cause eutrophication, hindering self-cleansing of water, and are very poisonous to the environment in the water. In addition, most of the above detergents have an atom group, e.g., alkyl group or methyl group, in a side branch, or have benzene nuclei, so they had to go through a sulfate processing or a sulfonate processing, but still failed to exhibit sufficient cleansing capacities requiring a lot of extra additives for more efficient cleansing, which in turn resulted in serious pollution in both land and water.
The inventors then turned their interests to linear type detergents having fatty acid surfactants as base since they are known to be very safe for the ecosystem. Unfortunately, most of the fatty acid surfactants slowed down natural decomposition by microorganism and were seriously harmful for a human body. This discovery was known to the inventors by observing that those fatty acid surfactants are produced by adding ethylene oxide during a addition processing, or adding sulfuric acid or chloro sulfonic acid during an ester processing, so they naturally have an ethylene linkage in their condensate. The condensate then polymerize with other organic sieve in the ecosystem or initiate secondary addition reactions that consequently inhibit the decomposition by microorganism.
Therefore, as an attempt to solve the problems described above, the inventors first tried to produce a specific active colloidal particle that was prepared by sintering many kinds of inert inorganic compounds at a high temperature to remove any impurities and make purified colloidal particle. In this matter, they succeeded to decompose contaminated organic materials, and to promote reduction of atoms in organic materials through an absorption-separation, thereby securing ecosystem""s safety. Further, the surfactant containing the above specific active colloidal particle had a greatly reduced harmful component compared to the conventional detergents. In result, the inventors succeeded to produce a new detergent for improving cleansing effect, and at the same time, being safe for a human and more safe and environmentally-friendly.
A method for manufacturing active components of collide according to the present invention is now explained in more detail by referring to the examples below, which are not intended to be limiting. Unless specified, the percentage indicates a percentage by weight. Invention conditions, for example, composition ratios or temperature ranges and so on, can be practiced by a person with an ordinary skill within the limit that the objective of the present invention is not changed.
Synthesis of Colloid Aluminum Silica Gel
To 25 wt % of sulfuric acid was dissolved aluminum hydroxide, Al(OH)2.xH2O (molecular weight: 77.99), that consists of 21.02% of aluminum oxide (Al2O3), 41.65% of silicic acid (SiO2), 5.48% of potassium (K2), 2.70% of red iron oxide (Fe2O3), 20.85% of sulfuric acid (H2SO4), and 0.63% of water. Then, potassium sulfate (K2SO4) was added, and the mixture was stirred at a low temperature within a range of from 68xc2x0 F. to 77xc2x0 F. to produce soluble aluminum double salt, i.e., K2SO4.Al2(SO4)2.24H2O. In order to remove any impurities in the compositions, the soluble aluminum chelate was continuously stirred at a temperature of 176 to 185xc2x0 F., and an addition reaction was proceeded by slowly dropping 0.1% of enzyme, (Na2)2CO. In result, remaining impurities was greatly reduced, and high quality of potassium aluminum sulfate (potassium alum) with a high purity and density was obtained. The relevant chemical equation and products are illustrated below:
2Al(OH)3+3H2SO4xe2x86x92Al2(SO4)3+6H2O 
Al2(SO4)3+K2SO4+24H2Oxe2x86x92K2SO4.Al2(SO4)2.24H2O 
Here, the product was heated and condensed at 176xc2x0 F., and transferred to a flask to be stirred and was cooled. Then, the compositions were put into a centrifuge to be subjected to dehydration processing, and a hot concentrator to be subjected to a heat condensation at a temperature of 140xc2x0 F. for four hours. The compositions lost 18 molecules of hydrate and produced SO2 instead. The product was decomposed as white anhydrous aluminum oxide and potassium sulfate to yield the material (specific gravity: 1.758, melting point: 110xc2x0 C.) illustrated below:
K2SO4.Al2(SO4)3xe2x86x92Al2O3+3SO3+K2SO4 
Prior to the reaction, potassium alum (K2SO4.Al2(SO4)2.24H2O) was mixed with aluminum silicate (Al2(SO2)4) in a ration of 1:3 by weight, and added was water to compose 24 water salts (24H2O) alkali metal polysilicate-sulfate chelate. The resulting mixture was slowly precipitated at a low temperature of 59xc2x0 F. and produced pectograph of aluminum silicate sieve. Here, the pectograph indicates precipitated and dehydrated sol in colloid solution.
The pectograph of the aluminum silicate sieve consists of 53.95% of SiO2, 1.02% of Al2O3, and 35.15% of H2O, and the relevant reaction is illustrated below:
2Kal(SO4)2.12H2O+3Na2SiOAl2(SiO3)3+3Na2SO4+K2SO4+12H2O 
In order to improve absorption of the pectograph of the aluminum silicate sieve, 0.3% of light magnesia (MgO), 0.15% of iron oxide (Fe2O3), 3% of calcium hydroxide (Ca(OH)2), 1.75% of sodium hydroxide (NaOH), 0.10% of potassium hydroxide (KOH), and 35% of distilled water were added and stirred in sequence to produce chelate. The chelate was put into a tank and impurities therein were removed using a cleaning filter. Then, the chelate was placed in a spray dryer, and contacted with hot air through a heated air valve having a temperature range of from 302xc2x0 F. to 410xc2x0 F., connected to a cylinder to produce dried microsphere. This dried microsphere was placed in a melting furnace and fused at a temperature within a range of from 1202xc2x0 F. to 1562xc2x0 F. The melted microsphere was then cooled and hardened. To this microsphere, diluted sulfuric acid was added to prepare highly absorptive sieve. The sieve was twice cleansed using 10% of ammonia solution (NH4OH) to be neutralized, and heated at 140xc2x0 F. to be dehydrated and dried. The dried sieve then went through a vapor treatment, and was crushed and powdered. Using a colloid mil, this powder formed sieve having a particle size less than 1 xcexcm, and in result, highly absorptive aluminum silicate molecular sieve was obtained.
The aluminum silicate sieve was dissolved in distilled water having 2.5 times of the sieve by weight. To the solution, 25% of sodium hydroxide was added by weight of the distilled water. The mixture was vapor heated at a temperature within a range of from 158xc2x0 F. to 284xc2x0 F., and was matured. Through a polymerization processing around 140xc2x0 F., the mixture was matured to heel with a high density. To this matured heel, slowly added was diluted sol for polymerizing precipitation, which was prepared by diluting sodium silicate (Na2O.3SiO2.xH2O) that passed through a cation exchange resin layer. Again, the resultant passed through an anion and cation exchange resin layer in order to prepare highly pure and consistent colloidal silica gel. Therefore, using a colloid mill employed a corundom stone, the consistent aluminum silica gel was crushed, and sprayed at a high pressure using especially a colloid mill having the structure of air turbulent to be subjected to a turbulent diffusion processing. When the turbulent diffusion processing was completed, the aluminum silica gel was compressed on a screen with below minus 14 mesh to yield uniform aluminum silica gel The final products, in other words, uniform microsphere colloidal active particles, which went through all the above processes, have characteristics both of silica and alumina and at a low temperature, and they possess complex functions of zeolite of alumina gel crystal. The colloidal active particles form a relatively uniform granularity having a particle size of a diameter within a range of from 1 micronmeter to 1 nanometer For the above particular case, the diameter of the colloid particles was 1 nm. Also, it was discovered that these activated colloidal particles retained molecular chaos due to strong free energy in a solution. The thermal energy, that is, brownian force, of the particles was measured as following:
(Applied force: xcex1=1 xcexcm, xcexc=10xe2x88x923 kg/ms, U=1 xcexcm/s, xcfx81=103 kg/m3, xcex94xcfx81/xcfx81=10xe2x88x922, g=10 m/s2, Aeff=10xe2x88x922 Nm, "xgr"=50 mV, xcex5=102)
Electrical force/Brownian force aeo"xgr"2/KT≈102 
Attractive force/Brownian force Aeff/KT≈1
Brownian force/Viscous force KT/xcexcUa2≈1
Gravity/Viscous force xcex13xcex94Pg/xcexcUa≈10xe2x88x921 
Initial force/Viscous force xcexca2U2/xcexcUa≈10xe2x88x926 
wherein, wherein, xcex1 is length; K is Boltzmann constant (1.381xc3x9710xe2x88x9223 J/K); T is absolute temperature; additivity (Van der Waal""s force on an atom or a molecule generates between electron microscope body); 0(Aeff/a), Aeff is Hamaker constant, aeo"xgr"2 is colume law, E is a dielectric constant of a fluid; EO is a dielectric constant in free space (8.88xc3x9710xe2x88x9212 C/Vm), "xgr" is an electron potential of a particle; U is viscous force on a particle moving with any velocity; O(xcexcxcex1U) is a median value of viscosity; O(a2p2U2) is the law of inertia of Stockes; and, O(a3Pg) is gravity on a particle.
Therefore, the above again confirms that the activated colloidal particle of the present invention exhibits thermodynamic activity in molecular chaos to be accordance with Brownian mathematical theory.
So far, any one has ever found a method for manufacturing multifunctional activated colloidal particles using a mixture of aluminum silicate, magnesia (MgO), iron oxide (Fe2O3), calcium hydroxide (Ca(OH)2), sodium hydroxide (NaOH), and potassium hydroxide (KOH), and a surfactant using the same.
Synthesis of Alkanolamine Condensate Using 12-hydroxy-cis-9-octadecanoic Acid, Alkanolamine and Water
A homogenous compound was prepared by mixing botanical ricinoleic acid extracted from caster oil having a formula of C16H34O3, equimolar amount to 1 mole of diethanolamine having a formula of HN(CH2CH2OH)2, and the same amount of water. The produced slurry was distilled off at an atmospheric pressure at 175xc2x0 C. to 180xc2x0 C. to remove any remaining reactants and in result, consistent surfactants were obtained.
The inventors have been motivated ever since they found that the conventional fatty acid soft type detergents that had been developed as an alternative for petroleum type detergents were also stimulant to a human skin, and were not biodegradable fast enough so that they could not provide standard optimum conditions for decomposition by microorganism. Moreover, the fatty acid type detergents employ alkanolamide as a base component which causes an addition reaction with highly reactive ethylene oxide or ethylene chlorohydrine during an addition processing and produces ethylene adduct at a high temperature. This condensate was found to be very harmful to a human and became a malignant substrate forming polymers through an ethylene linkage with other organic substances in the ecological environment. In order to solve these problems, the inventors have developed a new surfactant functional substance that was produced without an addition processing wherein ethylene oxide or ethylene chlorohydrine was typically employed.
The chemical reaction equation for the aforementioned surfactant functional substance is illustrated below:
RCO2H+HN(CH2CH2OH)2xe2x86x92RCON(CH2CH2OH)2+H2O 
The surfactant functional material as described above was obtained by reacting fatty acids, that is, 12-hydroxy-cis-octadetanoic acid, with alkanolamine and water to induce an oxidation of a hydroxyl group (OHxe2x88x92). In result, the mixture produced water-soluble salts with an ability of a surfactant. Taking advantage of this characteristic, the inventors introduced a new detergent using the above material as a component, which no one has ever found before.
Synthesis of a Specific Surfactant for Forming Spherical Monodisperse Colloid Micell
A homogeneous compound was prepared from a homogenizer by employing an nonionic surfactant of iso octylphenoxy polyoxy ethylene ethanol, a kind of ester of polyhydric alcohol and fatty acids having a formula of (CH3)3CCH2C(CH3)2C6H4O(OC2H4O)7(C2H4OH); a nonionic surfactant of p-tert-octylphenoxy polyethoxy ethanol having a formula of (CH3)3CCH2C(CH2)3C6H4O(CH2CH2O)XH; an nonionic surfactant polyoxy ethylene having a formula of HOCH2(CH2CH2O)nCH2OH; and distilled water by several times of weight. The mixture was then sprayed at a high pressure to form microhallowsphere, and heated by vapor for controlling moisture therein, which consequently condenses the density of the mixture, to obtain a particular surfactant that can form spherical monodisperse colloid micell.
Synthesis of Phycocolloid with a High Purity and Consistency for Ionizing Strong Negative Charge
The present invention provides a new form of protecting colloid.
A discovery has been made to an ascidiacea hormone in the ocean, i.e., male plant spermatia, which secretes particular kinds of metabolites and ionizes strong negative charge. A protecting colloid was made out of the mucilage of this hormone. The protecting colloid was known to stabilize the activities of unstable colloidal particles in an electrical field by helping the colloidal particles to be dissolved in a solution.
In consideration with that the polyaluminum silicate colloidal particles tend to be unstable in a solution, a protecting colloid with appropriate functions, especially stabilizing the colloidal particles, would be more than welcomed.
In order to manufacture the protecting colloid according to the present invention, first of all, a kind of alga, i.e., brown seaweed, which grows at a cold temperature in the deep sea was dried off through a natural seasoning in the shade within a temperature range of from 10xc2x0 C. to 15xc2x0 C. It was deposited in limewater to remove grease and impurities therein, and neutralized by reacting with an acid. Then, it was settled in the freshwater to be washed and was exposed to sunlight for manufacturing table-bagged seaweed. To this processed seaweed, water as much as 30 times by weight (wt %) and citric acid were added, and the mixture was heated at 212xc2x0 C. to 284xc2x0 C. to form a gel. Next, the resulted gel was put into a spray dryer having the construction of high pressure spray dryer system for controlling moisture therein, and again extruded to a screen with a mesh below xe2x88x9214. In this manner, the phycocolloid with a very high purity and consistency for ionizing strong negative charge was prepared.
The following are the physical properties of the phycocolloid:
mp: 132xc2x0 C., den(g/cm3): 153920, Solubility (nd):H2O 4 eth 1; bz1
thermodynamic properties: xcex94fHxc2x0/kJmolxe2x88x921=xe2x88x921263.0
Synthesis of a Novel Surfactant
By combining the surfactants described above, the present invention provides a novel surfactant with activated colloidal particles. The new surfactant consists of 8 to 12 wt % of colloidal active particles made of polyaluminum silicate; 5 to 8 wt % of alkanolamide condensate; 3 to 3.5 wt % of iso octylphenoxy polyoxyethylene, a nonionic surfactant of an ester of polyhydric alcohols and fatty acids; 2 to 2.3 wt % of a nonionic surfactant, p-tert octylphenoxy polyethoxy ethanol; 2.2 to 3 wt % of natural phycocolloid extract; and, 70.90 to 79.30 wt % of distilled water.
The surfactant of the present invention is not harmful to a human and the ecosystem since it contains greatly reduced amount of chemicals that used to cause environmental problems. In other words, the surfactant where specific physical properties were added upon countervails the disadvantages of the conventional surfactant in washing ability. No one in the industries has not yet found this new surfactant having specific physical properties and improved washing ability despite reduction of chemical factors necessary for washing.
One might assume that if the surfactant of the invention is dispersed in the water, it might not readily dissolve in the water due to the long hydrocarbon chain therein originated from an ester linkage of long ring-chained fatty acids and glycerin of functional groups in the surfactant, that is, alkanolamide condensate molecules and nonionic surfactant molecules. However, since the surfactant of the invention has hydrophilic groups, e.g., xe2x80x94OH, xe2x80x94COOH, xe2x80x94NO2, xe2x80x94NH2, at the end of each molecule, it easily dispersed and ionized in the water. Thus, when the concentration of molecules exceeds a critical micelle concentration, the molecules form a stable and soluble unimolecular film. In addition, when the unstable activated colloidal particles aforementioned disperse in a surfactant solution at a greater concentration than that of a critical micell concenration, water molecules in the water bond with these particles on the surface, namely, the unstable activated colloidal particles are hydrated and become the surface of hydroxyl groups. This hydroxyl group bonds with H+ in the water, such as, xe2x80x94OH+Hxe2x86x92OH+2, and molecules in the water change, such as, OH+OHxe2x88x92xe2x86x92Oxe2x88x92+H2O. Therefore, the unstable particles are absorbed to micell colloid of a surfactant, so free energy gets decreased and stabilized hydration can be maintained. At this time, the surfactant charge of colloidal particles in the solution is equivalent to charge of the opposite sign ion in the liquid, consequently forming an electric double layer around the particle. On the other hand, the phycocolloid extracted from a natural seaweed contains D+ mannose as a main component that has more than 9 of glycosidic bond, and is a kind of polysaccharides having botanical polysaccharide compound of a formula (C6H12O6)n.
Accordingly, the detergent of the present invention are surfactant compositions with much improved consistency, absorption and ion exchange function, which consists of carbon, hydrogen and oxygen, and is composed of consistent colloidal particles having strong negative charge.
The phycocolloid is added into the cleansing liquid, or the detergent, containing colloidal particles prepared in the invention to ionize strong negative charge ["xgr"1, "xgr"2 greater than K (electrolytic concentration of a solution), and to change zeta ("xgr") potential of the dispersed colloidal particles so that the stable colloidal particles can be stabilized. Moreover, in the electrostatic field, the particles"" brownian motion force gets much better and this consequently doubles the detergent""s performance of shaking dirt on the laundry. Thus, the detergent containing physocolloid of the present invention has much improved washing ability, and further the colloidal particles therein are equipped with excellent electrolytic properties and absorption, so they are well prepared for buffing the separated dirt""s re-precipitation.
The above described technology for building up electrolytic properties of strong negative charge around phycocolloid to help a surfactant perform washing much better by means of colloidal particles"" organic supplement, wherein the particle has oxidation crystal structure of silicic acid and aluminum that are supplied as washing materials, has not yet been published.
When the surfactant of the present invention is dispersed in the water, the colloidal particles absorb surface charge and proceed very powerful random movement one another. Later, the particles directly intrude into dirt in order to separate oil, grease and earth from the laundry, and perform highly efficient and activated washing. In addition, the surfactant of the present invention, since it takes an advantage of physical properties of the activated colloidal particles to compensate a great amount of required builders in other detergents and surfactants in general, is more appropriate for protecting the ecosystem and maintaining environmentally-friendly safety This washing mechanism of the invention is, therefore, very distinctive from operation mechanism of the conventional detergents.
Using water as a medium, the surfactant of the present invention allows the activated particles therein to perform particular physical and chemical functions. Wherever there is a certain amount of moisture for the particles to be activated, they perform excellent washing regardless of the kind or quality of water, such as, light water, fresh water, or salt water. Further, the surfactant by itself does not contain pollution and toxicity factors, e.g., phosphate, sulfate, nitrate, nitro triacetic acid (NTA), enzyme, corrosive agent and so on, and linkage for polymerization with other organic substances that are dissolved in the ecosystem. Thus, the surfactant easily captures light water ions, e.g., calcium (Ca++), magnesium (Ma++), iron (Fe++) and so on, and does not create any precipitate in any kind of light water.
The surfactant of the present invention also contains a little amount of colloidal-active semiconductor particle as an electro deposit photocatalyst to form compatible micell in organic surrounding, so their mutual organic activity absorbs ultraviolet and transits ozone for a rapid decomposition in the water. In result, the surfactant causes a reaction between ozone and a photon, from which a highly reactive hydroxyl group for promoting photolysis is produced.
In other words, the photon induction of colloidal-active semiconductor particle produces photo-oxidation derivatives and further detoxicated hydroxyl groups, which react with non-reactive molecules in the solution for accelerating oxidation-reduction of organic substances.
In the meantime, the inventors found that the colloidal-active semiconductor particle as an electrro deposit photocatalyst can be used for preparing activated molecular sieve by preparing dehydrated and dried CdS sol, which is a mixture of approximately 104M of cadmium chloride of a formula Cd(ClO4)2.26H2O, tetrahydraofuran ring type ether of a formula C6H8O, long ring-chain type alkanethiol (RSH), and sulfureted hydrogen. The physical properties of this CdS sol are now explained below.
Diffusion Data of CdS (Cadmium Sulfide) Sol Semiconductor
Frequency factor, D. (cm2/s): 1.6*102 
Activation energy, Q (eV): 2.05
Temperature range (xc2x0 C.): 800-900
Thermodynamic Measurement:
Molar enthalpy (heat) of formation at 298.15K in K/mol:
xcex94fHxc2x0/KJ molxe2x88x921=xe2x88x92161.9
Molar Gibbs energy of formation at 298.15K in K/mol:
xcex94fGxc2x0/KJ molxe2x88x921=xe2x88x92156.5
Molar enthalpy at 298.15K in J/mol K: Sxc2x0/J molxe2x88x921 Kxe2x88x921=xe2x88x9264.9
The photocatalyst CdS can have compatible colloidal-active particles in organic surrounding by a long chained alkanethion in tetrahydrofuran, and is prepared by cadmium ions together with H2S in the tetrahydrofuran. These particles exhibited a tendency to decrease in contrast to the increase of thiol. The mean diameter of CdS particles is influenced by the increase of thiol concentration, and is determined by the equation, i.e., log d=1.32-1.13 log c. In the equation, d(nm) indicates the mean diameter, and c(M) indicates thiol concentration.
The above cadmium sulfide colloidal sol forms a very strong binding with thiol on the surface to make thiol group containing sulfide ions for instance, and the stabilized cadmium sulfide by thiolate is very sensitive to ultraviolet in the solution and has light absorption fluoresce. Further, the CdS sol continues to organic activation with the dispersed colloidal particles, absorbs photos, transits and decomposes ozone, and makes highly reactive detoxicated hydroxyl group (OHxe2x88x92) for photo-oxidation. Photo-oxidation of positive holes in CdS particles due to light absorption and electrons of thiolate anions and their oxidationxe2x80x94reduction, can explain the photolysis mechanism.
In this case, CdS particles that are stabilized by thiolate actively decompose ultraviolet into the solution as long as oxygen or ozone is present. Therefore, at the absence of oxygen or ozone, the CdS particles lose stabilizing group and cause agglomeration forming large particles, thereby deterring more efficient dispersion of the absorbed ultraviolet. This is probably because of the oxidation-reduction of the positive holes in CdS particles and the thiolate anions, which decreases thiolate chains and creates unstable surrounding for CdS colloidal particles. The elementary process thereof is as follows:
The light absorption agglomeration number, n, of a colloidal particle having one stabilized thiolate anion (RSxe2x88x92) leads electron holes in pairs.
((CdS)nRSxe2x88x92)xe2x86x92(CdS)nRSxe2x88x92(exe2x88x92)(h+))xe2x80x83xe2x80x83(1) 
The major reaction involves a re-bonding of carriers that are either radioactive or free of light-emission.
exe2x88x92+h+xe2x86x92hxcexdfluorescence (thermalization)xe2x80x83xe2x80x83(2) 
This shows an oxidation of thiolate anions. Meanwhile, thiol radical is emitted from colloidal particles.
(CdS)nRSxe2x88x92(exe2x88x92)(h+))xe2x86x92(CdS)nexe2x88x92+RSxe2x88x92)xe2x80x83xe2x80x83(3) 
The remainder of electrons can form cadmium metal and a dimer for forming either thiol radical or disulfide.
2(RSxe2x88x92)xe2x86x92(RS)2xe2x80x83xe2x80x83(4) 
An electron from another colloidal particle can stabilize the thiol radical that is produced by emission of colloidal particles.
(CdS)nRSxe2x88x92(exe2x88x92))xe2x86x92(CdS)n)+RSxe2x88x92xe2x80x83xe2x80x83(5) 
In this manner, a phytolysis experiment of CdS colloidal sol was conducted under various illumination times in the presence of oxygen, and absorption spectrum therefor was xcex greater than 329 nm.
In the present invention, Cd(ClO4)2.26H2O having 10xe2x88x924 to 10xe2x88x923 M was dissolved in tetrahydrofurane, later mixed with thiol, and to the mixture, H2S was injected through septum. Then, the solution was violently stirred. For the photolysis experiment, xenon lamps from various filters were employed. As for the eluent of HPLC (high pressure liquid chromatography), the mixing solution of 10xe2x88x923 M of Cd(ClO4)2.26H2O, tetrafuran solution, and 10xe2x88x922 M of thiol solution was used.
According to the measurements of the above experiment, absorption materials (5 xcexcm) by chromatography were 500xcex of nucleaosil for the first column and 1000xcex of nucleosil for the second column. For the measurement of nucelosil without sulfureted hydrogen was 400xcex. The area of a column was 12 cmxc3x974 mm. For the chromatography of the experiment, 1xc3x9710xe2x88x923 M of Cd(ClO4)2.26H2O and 2xc3x9710xe2x88x924 M of H2S were added. Also, to the H2S, various amounts of hexanethiol were additionally added. In an experiment as above, as the thiol concentration (thiol, C6H13SH) gets higher, photoluminiscent strip indicators for CdS colloid absorption spectrum transferred from yellow to blue, and colorless at the highest concentration. This phenomena confirms that light absorption of cadmium sulfide sol is proportional to thiol concentration because the particles therein become smaller due to the increased thiol concentration, being in a better position to absorb light. Therefore, disulfide was exhibited in a methyl silicon column of gas chromatography, and this is because of light absorption of CdS particles.
Although a starting point of absorption and a diameter of a particle were measure through diverse experiments using an extrapolation method, the operation of thiol exhibited a similar particle growth limit found in telermorization of polymer chemistry. Accordingly, the correlation factor between granularity of particle size and concentration of terminating agent is calculated from straight lines obtained by double logarithmic plot using a particle""s diameter, d(xc3x85), and thiol concentration ratio c(M) as follows:
Log d=K1K2 
wherein K1 is 1.32 and K2 is 0.13.
Similar measurements were obtained from didecanethiol, octacdecanethiol, and 1,9-nonanedithiol, which have the value of K1 between 1.25 and 1.34 and that of K2 between 0.12 and 0.14. This tendency again confirms that granularity of a particle decreases as thiol concentration increases according to HPLC (high pressure liquid chromatography). Therefore, large particles are only observed during the short elution of chromatography. The colloidal particle retained stability for several weeks, and the absorption and fluorescence thereof were not affected at all even reflux was done at 90xc2x0 C. for several hours. In the meantime, if no oxygen was present, the degree of light absorption rapidly decreased by approximately 10%, and cadmium sol made of strong bonding of alkanethiols was dissolved in an organic material but showed no changes against heating at 90xc2x0 C. in terms of the affinity in the organic medium. These kinds of phenomena could be obtained because thiol functional groups are very tightly bonded to colloidal particles. In other words, a Cd2+ ion has a strong bonding with a thiolate anion. In contrary, in the presence of oxygen, according to the mechanism for decomposing photoanodic of CdS colloid, the CdS particles absorb ultraviolet to react with trapped hole where an elctron is captured to react with oxygen to produce O2, and form highly reactive hydroxyl groups, deterring photo-oxidation. Here, the trapped hole is an anion of oxidized S radical during a reaction with O2 or O2xe2x88x92, in order to chemically form sulfite and finally sulfate ions.
The surfactant of the present invention very easily decomposes by microorganism even at a relatively low temperature. Thus, it is possible to accomplish the almost complete decomposition by microorganism within several days. The biodegradation rate was tested on the detergent of the present invention when used in the water of 20xc2x0 C. In result, 33% of the detergent was decomposed within 24 hours, 82% in 5 days, and 98.5% in 7 days.
B.O.D. (Phenylazide method): 5 days, 81.250 mg/l, ultimate 136500 mg/l (K=0.104)
The above biodegradation rate exceeds the maximum standard value stipulated by Environmental Protection Agency (EPA) in the United States. Thus, there is high expectation on this new form of detergent from a viewpoint that it would make a great contribution to the protection of water resources.
The product of the present invention eliminates too much use of chemical compounds, but is capable of activating useful qualities of colloidal particles for the washing detergent. Thus, it aims to minimize effluent or wastewater due to the detergent, and further to completely eliminate any toxicity therein that harms underwater life.
Moreover, the product of the present invention can be commercialized in most of industries since it is applicable for both alkali and acid. Especially, hydrophobic colloid of the detergent according to the invention is formed of a long hydrocarbon tail and a polarized head, thus, if the concentration increases, micelle crystallizes as an aggregate. At this time, the hydrocarbon tail heads toward the inside of micell and the polarized part touches water.
More micells are built by interaction between hydrocarbon tails, and each micell replaces hydrophobic surrounding with hydrophilic surrounding. And, the hydrophilic solid obstacle around the micell often interrupts the aggregation.
Critical micellar concentration of the detergent solution of the present invention, or the concentration factor, is 0.08xc3x9710xe2x88x923, which is measured by table surface tension law at 25xc2x0 C.
The typical micell of the surfactant of the invention has approximately 50-60 of soap molecules. Hence, the soap molecules in one micell are the ones that dissolve even considerably insoluble dirt in the solution by inviting them to the inside of the micell. Besides, the molecules easily dissolve oil-bearing compounds including organic substances, e.g., halogenated compound, MEK (methyl ethyl ketone), heptane and so forth, wax, complex alcohol, drinks like milk or juice, and substances that do not dissolve in other clear detergent solutions.
According to the surfactant of the present invention, the initial sol concentration having one minute of half life is 1.4xc3x97109 in the water, if no obstacles for assembly are allowed. The maximum of colloid of the surfactant is 5xc3x9710xe2x88x925 for a radius of a particle, and 1.4xc3x97109 of particles occupy 0.07% of space per cc.
In addition, particles of the surfactant of the present invention are usually electrically charge in sol and they are manifested through electrophoresis. Their physical operation is more like an electric phenomenon, but more interestingly, they dissolve substances that didn""t dissolve in other kinds of detergent solutions, because the particles act more aggressively upon the hydrophillicity or affinity of water. A measurement on the potential of H+ and OHxe2x88x92 is measuring potential ions against oxidized sol containing a lot of metals and particles like carbon that oxidized table surface although they do not seem to be oxidants on the table surface itself. The size of micell in the surfactant of the invention is approximately 10xe2x88x925-10xe2x88x927 cm.
The present invention is now explained in more detail with reference to the accompanying examples. Unless specified otherwise, every percentage throughout the specification indicates the percentage by weight (wt %).